Coloration of materials made of or containing organic derivatives of cellulose



Patented Jan. 29, 1935 COLORATION OF MATERIALS MADE OF OR CONTAININGORGANIC DERIVATIVES OF CELLULOSE George Holland Ellis, Spondon, nearDerby, England , assignor to Celanese Corporation of.

America, a corporation of Delaware No Drawing. Application February 5,1932,

Serial No. 591,235

8 Claims.

This invention relates to the coloration, by dyeing, printing,stencilling or other methods of artificial filaments, threads, fabrics,films, or other products or materials made of or containing celluloseacetate or other organic derivatives of cellulose.

This application is in part a continuation of my co-pending applicationNo. 98,614 filed March 30, 1926.

Ihave found that colorations obtained on said materials with the aid ofdyestuifs of the anthraquinone series containing an aliphaticacidvlamino group in an iii-position and an amino, alkylamino -orsubstituted alkylamino group in the (ii-position para to the aforesaidaposition, in adidtion to pomessing the advantage that they yield thevery valuable red to bluish-red or violet colorations on the materials,have an extraordinary fastness far superior to the fastness of suchbodies on other materials, such as wool or cotton, and superior also tothe colorations produced with the aid, of simple aliphatic acidylaminoanthraquinones, i. e. bodies which do not possess the amino groups inthe 1:4 position, one of which is substituted by an aliphatic acidylgroup. For convenience the aliphatic acidyl group will be hereinafterreferred to as an alkacyl group.

The dvestufis to be appliedin accordance with the present invention havean alkacyl amino group in the 1- position and an amino, alkvlamino orsubstituted alkylamino group in the 4- position. They may contain anyother desired substituent'- groups, such as amino, hydroxy, chlor,methyl and the like, but-preferably they should contain no sulphogroups. The aliphatic acid -residue substituted on the amino group inthe 1- position may be derived from any desired aliphatic acid, forexample acetic acid, propionic acid, oxalic acid, succinic acid or thelike. The dyestuffs have the general formula 0 NR R:

NRiR;

wherein R1 is an aliphatic acidyl group and R2,.

R: and R4 are hydrogen, alkyl or substituted alkyl groups. The remainingpositions in the anthraquinone nucleus may be substituted orunsubstituted.

The following are examples of suitable dyestuffs which may be applied inaccordance with the present invention:-

Shade yielded Dyestufl i on cellulose acetate l-acetylamino-i-aminoanthraquinone Red. l-acetylamino-i-methylamino anthraquinone Bluish-red.

l-acctylamino-i-hydroxycthylamino anthraquinone. Do.

0 NH. 00. OH:

I 0 N H. C23 0 The dyestuffs may be applied to the materials in anysuitable manner by dyeing, printing, stencilling or other methods. Iprefer to apply them in the unreduced state and in aqueous dispersion,since they are for the most part insoluble in water. They may be reducedto the state of aqueous dispersion (a) by so-called colloidal grindingor milling with or without assistants, (b) by dissolving them in asuitable solvent, such as acetic acid or acetic acid and alcohol, andpouring the resulting solution into an aqueous bath or into water,preferably containing a protective colloid, for example glue, and/or adispersing agent, and (c) by treating them with suitable dispersingagents so as to effect their dispersion in aqueous media. Such treatmentmay, for example, involve a pretreatment of the dyestuff with a more orless concentrated dispersing agent and subsequent dilution of thedispersionobtained with the aid of water, preferably containing a smallamount of soap or other dispersing agent and preferably hot. Suitabledispersing agents are, for example, those described in Patent No.1,618,413, and in particular the water soluble salts of higher fattyacids, such as oleic, stearic or palmitic acids, or the sulphonatedderivatives of higher fatty acids or their salts, as for examplesulphoricinoleic acid or sodium sulphoricinoleate; the carbocyclicdispersing agents of Patent No. 1,618,414, and in particular thenaphthenic acids or their salts and sulphonated naphthalene compounds orsalts thereof, for example the naphthalene formaldehyde sulphuric acidcondensation product or its sodium or ammonium salt; sulphonatedaromaticfatty acid complexes or compounds, for example sulphonatednaphthalene oleic acid or sulphonated benzene oleic acid,sulphonatednaphthalene ricinoleic acid, sulphonated phenol ricinoleic acid,

sulphonated benzene ricinoleic acid, or their alkali or ammonium salts;resin soaps; and other bodies having dispersing properties, such assulphite cellulose lye.

The dyestuffs may if desired be applied by vatting methods, and inparticular by vatting methods which involve the use of minimum amountsof caustic alkali or in which the alkalinity of the vat is suitablyreduced, as for example by the,

methods of Patent No. 1,716,720 (British Patent No. 262,506) involvingthe addition to the vat of hydroxy or polyhydroxy or simple ringsubstituted derivatives of hydroxy or polyhydroxy compounds of theisocyclic or heterocyclic organic series, such as benzene, napthalene,anthracene or pyrazol series and the like. Instead of adding the hydroxyor polyhydroxy bodies, for example phenol, cresols, xylenols, catechol,resorcin and the like, to the vat the vat may be made up with the sodiumor potassium salts of these compounds.

v The dyestuffs of the present invention may be applied to the.coloration of materials consisting wholly of cellulose acetate or otherorganic derivative of cellulose, for example cellulose formate,cellulose propionate, cellulose butyrate, cellulose nitro-acetate, ormethyl, ethyl or benzylcellulose, or to mixed yarns, fabrics or'othermaterials containing such organic derivatives of cellulose inassociation with other fibres, for example cotton or other yarns orfibres of the cellulosic type, whether natural or-artificial, wool, silkand so forth. Differential or uniform shades may be obtained inaccordance with the afinity of the dyestuffs for such other fibres ascompared with their aflinity for the cellulose acetate or other organicderivative of cellulose.

The following examples illustrate the coloration of cellulose acetategoods by the present invention, though they are not to be considered aslimiting the invention in any way:

Example 1 1 lb. of 1-acetylamino-4-amino anthraquinone bath is raised to75 80" 'C. in hour and maintained at this temperature hour.

The goods, which are now dyed a red or bluishred shade, are lifted, wellrinsed in soft water and dried or otherwise treated as desired.

Example 2 1 lb. of. 1-acetylamino-4-hydroxyethylamino anthraquinone isground to a fine powder and added with stirring to 6 lbs. of 50% aqueouspotassium sulphoricinoleate." The whole is heated to 80 0., withstirring, and when as homogeneous as possible it is diluted to tengallons with boiling soft water, and poured through a filter cloth intoa dyebath containing 300 gallons of soft water. 100 lbs; of celluloseacetate yarn in hank form are now entered, the bath is raisedto 'l5-80C. in hour, and maintained at thistemperature Y4 hour.

The goods, which are now dyed a bluish-red shade, are lifted, wellrinsed' in soft water, and dried or. otherwise treated as desired.

Example 3 1 lb. of l -acetylamino-4eamino anthraquinone is mille'd to afine paste with 9 lbs. of water in a "colloid mill". When asfinelyreduced as possible the paste so formed is added to a 300 gallondyebath to which has been added previously a solution of 10 lbs. of gluein water. The liquor is well stirred, and 100 lbs. of cellulose acetateyarn in hank form are now entered. -The temperature is raised to 75-80C. in hour and maintained at this temperature a further hour. The goods,which are now dyed the red or bluishred of Example 1, are lifted, wellrinsed in soft water and dried or otherwise treated as desired.

Example 4 1 lb. of l-acetylamino-4-methylamino anthraquinone isdissolved by boiling in 5 lbs. of glacial acetic acid. The hot solutionis now poured with vigorous stirring into 20 gallons of water. This isnow added to a 250 gallon dyebath at 50 C., and 100 lbs. of celluloseacetate yarn in hank form are entered. The temperature is raised to75-80 C. in /2 hour, and dyeing is continued at this temperature for 1hour.

The goods, which are now dyed a bluish-red, are lifted, rinsed well, anddried or otherwise treated as desired.

What I claim and desire to secure by Letters Patent is: v

1. Process for the coloration of materials comprising organicderivatives of cellulose, comprising applying thereto anthraquinonecompounds containing an alkacyl amino group in the 1- position and anamino, alkylamino orsuhstitutedalkyl amino group in the 4- position.

2. Process for the coloration of materials comprising organicderivatives of cellulose, comprising applying thereto unsulphonatedcompounds of the general formula o NEAR:

wherein R1 is an aliphatic acidyl group and Ra, R: and R4 are hydrogen,alkyl or substituted alkyl groups.

3. Process for the coloration of materials comprising cellulose acetate,comprising applying thereto anthraquinone compounds containing analkacyl amino group in the 1- position and an amino, alkylamino orsubstituted alkyl amino group in the 4- position.

4. Process for the coloration of materials comprising cellulose acetate,comprising applying thereto unsulphonated compounds of the generalformula 0 NRIR:

in the 1- position and an amino, alkylamino or wherein R1 is analiphatic acidyl group and R2, substituted alkyl amino group in the 4-position. R3 and R4 are hydrogen, alkyl or substituted alkyl 6. Processfor the coloration of materials comgroups.

prising cellulose acetate, comprising applying 7. Process for thecoloration of materials com- 5 thereto an aqueous dispersion ofunsulphonated prising cellulose acetate, comprising applying compoundsof the general formula thereto 1-acetylamino-4-amino anthraquinone.

O NRIR, 8. Process for the coloration of materials comprising celluloseacetate, comprising applying thereto an aqueous dispersion of1-acetylamino-4- 10 amino anthraquinone.

GEORGE HOLLAND ELLIS.

NR3R4

